WO2007105807A1

WO2007105807A1 - Method for production of conjugated polymer

Info

Publication number: WO2007105807A1
Application number: PCT/JP2007/055311
Authority: WO
Inventors: Seiji Oda; Takashi Kamikawa
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2006-03-13
Filing date: 2007-03-09
Publication date: 2007-09-20
Also published as: CA2644373A1; EP1997844A4; US20090048413A1; EP1997844A1; KR20080105107A; TW200804452A

Abstract

Disclosed is a method for production of a conjugated polymer. The method comprises the step of (A) contacting an aromatic monomer having at least two boron-containing functional groups with an aromatic monomer having at least two reactive functional group or (B) contacting aromatic monomers each having at least one boron-containing functional group and at least one reactive functional group with each other, both in an ether solvent in the presence of a palladium catalyst having a phosphine compound coordinated to palladium, cesium carbonate and 1 to 100 moles of water relative to 1 mole of the boron-containing functional group in the aromatic monomer.

Description

Production method of conjugated polymer.

Technical field

The present invention relates to a method for producing a conjugated polymer. Light

Background art

A conjugated polymer is a polymer having a delocalized 7T-electron system in part or all of the main chain of the polymer, and is used, for example, in the production of optical devices.

The process of reacting an aromatic boronic acid compound with an aromatic halide in the presence of a solvent, a water-soluble inorganic base and a palladium catalyst to produce the corresponding biphenyl compound is known as the “Suzuki Force Pulling Reaction”. (See, for example, Synthetic Communications, 11 (7), 513, 1981), and a method for producing a conjugated polymer using such a Suzuki coupling reaction is known. For example, US Pat. No. 5,777,700 discloses a method for producing a conjugated polymer using an aqueous sodium carbonate solution and a phase transfer catalyst. However, since a phase transfer catalyst is used, the operation for taking out the obtained conjugated polymer is complicated. In addition, Macromolecules 2003, vol. 36, 8986-8991 discloses a method for producing a conjugated polymer using a carbonated lithium aqueous solution. However, the weight average molecular weight (Mw) of the obtained conjugated polymer is often 10 or less, and there is a problem that it is difficult to obtain a high molecular weight conjugated polymer. Furthermore, US Pat. No. 6,943,929 discloses a method for producing a conjugated polymer using an aqueous cesium carbonate solution. The weight average molecular weight (Mw) of the resulting conjugated polymer is about 14, 0 It was as low as 0 0.

Disclosure of the invention

The present invention <1> (A) an aromatic monomer having at least two boron-containing functional groups and an aromatic monomer having at least two reactive functional groups, or (B) at least one boron-containing functional group and at least one An aromatic monomer having a reactive functional group is mutually bonded to a palladium catalyst in which a phosphine compound is coordinated with palladium in a ether solvent, cesium carbonate, and 1 mol of the boron-containing functional group of the aromatic monomer. A method for producing a conjugated polymer, which is brought into contact in the presence of 1 to 100 moles of water;

<2> The method for producing a conjugated polymer according to <1>, wherein the ether solvent is an aliphatic ether solvent;

<3> The method for producing a conjugated polymer according to <2>, wherein the aliphatic ether solvent is tetrahydrofuran;

<4> The method for producing a conjugated polymer according to any one of 1 to 3, wherein the phosbuin compound is a phosphine compound in which at least one alkyl group is bonded to a phosphorus atom; 5> at least one alkyl group A phosphine compound in which is bonded to a phosphorus atom is represented by the formula (I)

(In the formula, R ¹ R ² and R ³ each independently represents an alkyl group having 1 to 30 carbon atoms.)

<6> A method for producing a conjugated polymer according to <4>, wherein the trialkylphosphine represented by formula (I) is tricyclohexylphosphine. Production method;

<7> The method for producing a conjugated polymer according to any one of <4> to <6>, wherein 1 mol of the boron-containing functional group of the aromatic monomer is contacted in the presence of 1 to 75 mol of water;

<8> The method for producing a conjugated polymer according to any one of <4> to <6>, wherein 1 mol of the boron-containing functional group of the aromatic monomer is contacted in the presence of 1 to 45 mol of water;

<9> The method for producing a conjugated polymer according to any one of 1 to <3>, wherein the phosphine compound is a phosphine compound in which three substituted or unsubstituted aryl groups are bonded to a phosphorus atom; <10> A phosphine compound in which three substituted or unsubstituted aryl groups are bonded to a phosphorus atom is represented by the formula (II)

(Wherein R ⁴ , R ⁵ and R ⁶ each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. , 1, m and n each independently represents an integer of 0 to 5. When 1 represents an integer of 2 or more, R ⁴ may be different from each other, and when m represents an integer of 2 or more, R ⁵ may be different from each other, and when n represents an integer of 2 or more, R ⁶ may be different from each other.) The method for producing a conjugated polymer according to <9>, which is a triarylphosphine <11> The method for producing a conjugated polymer according to <10>, wherein the phosphine compound represented by the formula (II) is triphenylphosphine or tris (4-methylphenyl) phosphine; <12> a boron-containing aromatic monomer 1 to 25 moles of functional group <9> A method for producing a conjugated polymer according to any one of <11> to <11>;<13> an aromatic monomer having at least two boron-containing functional groups, at least two reactions An aromatic monomer having a functional group and an aromatic monomer having at least one boron-containing functional group and at least one reactive functional group are represented by the formulas (1) to (16):

f

TlCSS0 / .00Zdf / X3d .08S0T / .00Z OAV

(Wherein, X ¹ and X ² each independently represent a boron-containing functional group or a reactive functional group, R ^1Q represents a group not involved in the reaction, p represents an integer of 0 to 2, q represents an integer of 0 to 3, r represents an integer of 0 to 4, and s represents an integer of 0 to 5. When R ¹⁰ is plural, they may be different from each other. Two R ^ltJ bonded to the carbon atom to be bonded together may form a ring together with the bonded carbon atom, Y represents a group 16 element in the periodic table, and Z represents , 101, 1 S—, -N (R ²⁰ ) 1 or

/ \

R ²¹ V ²

Represents. Here, R ^2Q , R ²¹ and R ²² each independently represent a hydrogen atom or a group not involved in the reaction. ) The method for producing a conjugated polymer according to any one of <1> to <12>, which is any of the aromatic monomers represented by:

<14> The method for producing a conjugated polymer according to any one of <1> to <13>, wherein the reactive functional group is a chlorine atom, a bromine atom or an iodine atom;

15> The boron-containing functional group

(Wherein R ^3Q , R ³¹ , R ³⁴ and R ³⁵ each independently represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ³³ represents a divalent hydrocarbon group. .)

<16> The method for producing a conjugated polymer according to any one of <1> to <14>, wherein the divalent hydrocarbon group is an alkylene group having 2 to 6 carbon atoms. <15> A process for producing the conjugated polymer according to

<17> An alkylene group having 2 to 6 carbon atoms is ethane-1,2-diyl group, propane-1,3-diyl group, 2,2-dimethylpropane-1,3-diyl group or 2,3-dimethyl group. The method for producing a conjugated polymer according to <16>, which is a butane-2,3-diyl group. BEST MODE FOR CARRYING OUT THE INVENTION

The production method of the present invention comprises: (A) an aromatic monomer having at least two boron-containing functional groups (hereinafter abbreviated as “aromatic monomer M ¹ ”) and an aromatic monomer having at least two reactive functional groups (hereinafter referred to as “aromatic monomer M ¹ ”). Is abbreviated as “aromatic monomer M ² ” in an ether solvent with respect to 1 mol of a palladium catalyst in which a phosphine compound is coordinated to palladium, cesium carbonate, and 1 mol of the boron-containing functional group of the aromatic monomer. ~: A process for producing a conjugated polymer by contacting in the presence of L00 mol of water and (B) an aromatic monomer having at least one boron-containing functional group and at least one reactive functional group one (hereinafter abbreviated to aromatic monomer M ³⁾ to each other, in an ether solvent, a palladium catalyst a phosphine compound is coordinated to palladium, In this method, a conjugated polymer is produced by bringing cesium carbonate and 1 mol of boron-containing functional groups of the aromatic monomer into contact with each other in the presence of 1 to 100 mol of water.

The boron-containing functional group of the aromatic monomer M ¹ is as follows:

(Wherein R ³ °, R ³¹ , R ³⁴ and R ³⁵ each independently represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ³³ represents a divalent hydrocarbon group. Represents.)

Any group shown by these is mentioned.

Above all,

Is preferred.

R ³ R ³¹ , R ³⁴ and R ³⁵ are preferably unsubstituted alkyl groups having 1 to 6 carbon atoms.

Examples of the unsubstituted alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, Examples thereof include straight-chain, branched-chain, or cyclic unsubstituted alkyl groups having 1 to 6 carbon atoms such as a hexyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the substituent of the alkyl group include an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, and an aryl group having 6 to 12 carbon atoms such as a phenyl group.

Divalent hydrocarbon groups include ethane-1,2-diyl group, propane-1,3-diyl group, 2,2-dimethylpropane-1,3-diyl group, 2,3-dimethylbutane-1,2,3. — Alkylene groups with 2 to 6 carbon atoms, such as diyl groups, 1,2-phenylene groups, 1,3-phenylene groups, etc. 2-6 alkylene groups are preferred.

The aromatic monomer M ¹ has at least two such boron-containing functional groups and has one or more A monomer having an aromatic ring may be used, and a monomer having two boron-containing functional groups and having 1 to 6 aromatic rings is preferable. When the aromatic monomer M ¹ is a monomer having two or more aromatic rings, the boron-containing functional group may be bonded to the same aromatic ring or may be bonded to different aromatic rings.

The reactive functional group of the aromatic monomer M ^2, a chlorine atom, a bromine atom, eight androgenic atom such as iodine atom, triflate Ruo b methanesulfonyl group, a methanesulfonyl group halogen atom which may be substituted alkanesulfonyl group such as And arylsulfonyl groups such as a benzenesulfonyl group and p-toluenesulfonyl group, and a halogen atom is preferred.

The aromatic monomer M ² may be any monomer having at least two such reactive functional groups and one or more aromatic rings, having two reactive functional groups, and 1 to 6 aromatics. Monomers having a ring are preferred. When the aromatic monomer M ² is a monomer having two or more aromatic rings, the reactive functional groups may be bonded to the same aromatic ring or may be bonded to different aromatic rings.

The boron-containing functional groups of the aromatic monomer M ^3, the foregoing similar to boron-containing organic functional group of the aromatic monomer M ^1. Examples of the reactive functional groups, reactivity functionality of the aromatic monomer M ² The same thing as a group is mentioned.

The aromatic monomer M ³ may be a monomer having at least one boron-containing functional group and at least one reactive functional group and having one or more aromatic rings, and includes one boron-containing functional group and 1 Monomers having one reactive functional group and 1 to 6 aromatic rings are preferred. When the aromatic monomer M ³ is a monomer having two or more aromatic rings, the boron-containing functional group and the reactive functional group may be bonded to the same aromatic ring, or may be bonded to different aromatic rings. Also good.

The aromatic ring possessed by the aromatic monomer M ¹ , the aromatic monomer M ² and the aromatic monomer M ³ includes a benzene ring; a condensed aromatic ring such as a naphthalene ring, an anthracene ring and a fluorene ring; a furan ring and a thiophene ring. And a heteroaromatic ring such as a pyridine ring, a phenoxyazine ring, a phenothiazine ring, and a benzothiadiazole ring.

Specific examples of the aromatic monomer M ¹ , the aromatic monomer M ² and the aromatic monomer M ³ include Following formula (1)-(16)

(Wherein, X ¹ and X ² each independently represent a boron-containing functional group or a reactive functional group, R ^1Q represents a group not involved in the reaction, p represents an integer of 0 to 2, q represents an integer of 0 to 3, r represents an integer of 0 to 4, and s represents an integer of 0 to 5. When R ^1Q is plural, they may be different from each other. Two R ^1Q bonded to the carbon atom to be bonded to each other may form a ring together with the bonded carbon atom, Y represents a group 16 element in the periodic table, and Z represents , _〇一, — S—, one N (R ²⁰ ) '— or

— C—

/ \

R ²¹ V

Represents. Here, R ^2G , R ²¹ and R ²² each independently represent a hydrogen atom or a group not involved in the reaction. ) The aromatic monomer shown by these is mentioned.

Examples of groups that do not participate in the reaction include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, cyclopentyl, A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms such as a cyclohexyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, Linear, branched or cyclic alkoxy groups having 1 to 20 carbon atoms such as pentyloxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, cyclopentyloxy, cyclohexyloxy, etc., phenyl Group, 4-methylphenyl group such as 4-methylphenyl group, methoxycarbonyl group, etc. C2-C20 alkoxy groups such as ethoxycarbonyl groups, C6-C20 aryloxy groups such as phenoxy groups, acetyloxy groups, acetyl groups, propionyl groups, benzoyl groups, etc. Can be mentioned.

Examples of group 16 elements in the periodic table include oxygen, sulfur, and selenium.

Aromatic monomers M ¹ include 2, 2, 1 (9, 9-dihexyru 9 H-fluorene 1, 2, 7-diyl) bis (1, 3, 2-dioxapololene), 2, 2 '-(9 , 9-Dihexyl 9 H-Fluorene-1, 2, 7-diyl) Bis (1, 3, 2-dioxapolynan), 2, 2,-(9, 9 Dihexyl 9H-Fluorene-2, 7- Dill) Bis (4, 4, 5, 5-tetramethyl-1, 3, 2-dioxapololene), 2, 2, 1 (9, 9-dihexyl 9 H-fluorene 1, 2, 7-diyl) Bis (5 , 5—dimethyl—1, 3, 2, 2 dioxapolynan), 2, 2 ′-(9,9 dioctyl 9 H—fluorene 1,2,7 diyl) bis (1, 3, 2—dioxapololene), 2, 2 '-(9,9-dioctylru 9H-fluorene-1,2,7-diyl) bis (1,3,2-dioxapolynan), 2,2,1 (9,9-dioctylurine 9H-fluorene-1 2, 7-zyl) Dosu (4, 4, 5, 5-tetramethyl 1,3,2-dioxapololene), 2, 2 'one (9,9-dioctylru 9 H-fluorene-2, 7-zil ) Bis (5,5-dimethyl-1,3,2-dioxapolynan), 2, 2 '-(9,9-didodecyl 9 H-fluorene 1,7-diyl) Bis (1, 3, 2— Dioxapololene), 2, 2'-one (9,9-didodecyl-9H-fluorene-one 2,7-diyl) bis (1,3,2-dioxapolynan), 2,2 '-(9,9-didodecyl-9H- Fluorene-2,7-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxapololene), 2, 2,-(9,9-didodecyl-9 H-fluorene-2,7 —Diyl) Bis (5,5-Dimethyl-1,3,2-dioxapolynan), 2,2,1 (3,5-Dimethoxy-9,9-Dihexyl-9 H-Fluorene-2,7-Diyl ) Bis (4,4,5,5-tetramethyl-1,3,2-dioxapololene), 2,2'-one (9-octyl-9 H-carbazole-3,6-diyl) Bis (1,3,2-dioxapololene) 1, 2-benzenedipolonic acid, 2, 2, one (1,4 monophenylene) bis (5,5-dimethyl-1,3,2-dioxapolynan), 2, 2 '-(2,5-Dimethyl-1,4-phenylene) Bis (1,3', 2-Dioxapololene), 2, .2, One (2-Methyl-5-octyl-1, 4, —Phenylene) bis (4, 4, 5, 5-tetramethyl-1, .3, 2-dioxapololene),

2, 2, 1 (2,5-Dibutyl-1,4 monophenylene) bis (5,5-Dimethyl 1,1,2,2-dioxapolynan), 2, 2 'One [2,5-Bis (hexyloxy) ) -1,4-diphenylene] bis (5,5-dimethyl-1,3,2-dioxapolynan), 2,5-thiophene diboronic acid, 2,5-bis (1,3,2-dioxaborolene 2- Thiophene, 2,5-bis (4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolene 2-yl) Thiophene, 2, 5-bis (1, 3, 2-dioxapolynan 1) —Yl) thiophene, 2,5-bis (5,5-dimethyl-1,3,2-dioxapolynan-2-yl) thiophene, 4,4, biphenylpolonic acid, 1,1′-bis (4,4 4, 5, 5—Tetramethyl-1,3,2-dioxaborolene 2-yl) —4, 4 ′ —Phiphenyl, 1, 1 ′ —Bis (1,

3, 2, 2-Dioxaborolene 2-yl) 1, 4, 4 '— Biphenyl, 1, 1' — Bis (1, 3, 2-dioxapolynan-2-yl) 1, 4, 4'-Piphenyl, 1, 1 ' —Bis (5,5-dimethyl-1,3,2-dioxapolynan-2-yl) —4, 4 '—Phiphenyl, 5, 5,1 bis (4, 4, 5, 5-tetramethyl 1,3) , 2-dioxaborolen-2-yl) -2, 2, 1-bithiophene and the like. Aromatic monomer M ² includes 2,7-dibu-mouthed 9,9-dihexyloo 9 H-fluorene, 2,7-jibu-mouthed 9,9-dioctyl-9H-fluorene, 2,7-dibromo- 9, 9-Didodecyl 1 9H-Fluorene, 2, 7-Dichloro 1 9, 9-Dihexyl 1 9 H-Fluorene, 2, 7-Dichloro 1 9, 9-Dioctyl 1 9H-Laurelen, 2, 7-Dichloro 1 9, 9-didodecyl— 9 H-fluorene, 2-bromo-l 7—black mouth 9, 9-dihexilu 9 H-fluorene, 2-bromo-7-chloro-9, 9-dioctyl 9H—fluorene, 2-bromo-7— 1,9-didodecyl—9H-fluorene, 1,4-dibromobenzene, 1,3-dibromobenzene, 1,4-diib-mouse 2-ethylbenzene, 1,4-dibromo-2-methoxybenzene, dimethyl 2, 5—Dibromoterephthalate, 1 4-Dib mouth monaphthalene, 9, 10-Dibromoanthracene, 1,5-Dib mouth moanthracene, 3,5-Dibromopyridine, 1, 1, 1 dib ϋMo 4, 4, 1 pifenyl, 2, 5— Dibromopyridine, 1,4 1-dibo-mouse 2,5-dihexyloxybenzene, 1-bromo 4-cyclo-benzene, 1-bromo 4_chloro-toluene, 1-promo 4-chloro-2-propylbenzene 2, 5—Jib mouth mode 4, 1-phenoxybenzophenone, 2, 5—Dib mouth mode, 3—Hexylthiophene, 2, 5—Jib mouth mode, 3—Octylthiophene, 2, 5—Jib mode mode 3-Dodecylthiophene, 2, 5-Dichlorothiol 3-Hexylthiophene, 5, 5 'One Jib Mouth 2, 2, One Bithiophene, 5, 5, One Dibromo 1, 3, 3, —Dihexyloo 2, 2 '—Pithophene, Ν, Ν—Bis (4-bromophenyl) —4— (4 tert-Ptyl) aniline, N, N-bis (4 bromophenyl) —4 -1 (1-methylpropyl) aniline, N, N-bis (4-bromophenyl) aniline, N, N '— bis (4 1 Promophenyl) 1 N, Ν '-bis (4 1 η-butylphenyl) 1 1,4-diaminobenzene, Ν, N' 1 bis (4-bromophenyl) 1 bicyclo [4, 2, 0] 1 1, 3, 5 —Tolyen 1—3-amine, Ν, Ν, 1 bis (4 1-promophenyl) 1 Ν, Ν, 1 bis (4 butylphenyl) -1,4--daminobenzene, Ν, N '—bis (4-bromophenyl) ) —Ν, Ν, —Bis [4 (1, 1-Dimethylethyl) —2, 6-Dimethylphenyl] —1, 4-Diaminobenzene, 4, 7-Dipromo 2, 1,3—Benzochi Asia Zool, 4, 7-jib mouth moe 2, 1,3-benzoselenadiazol, 4, 7-bis (5-promo 2-cenyl) 1, 2, 1,3-benzochi asia zool, 4, 7-Bis (5-Bromo 4-Methyl-2-Chenyl) 1, 2, 1, 3-Benzothiadiazole, 4, 7-Bis (5 One Promo-3-Methyl-2-Chenyl) —2, 1 , 3—Benzothiadiazol, 3, 7—Dibromo— 1 0— (4— n-Ptylphenyl) — 10H—Phenothiazine, 3, 7—Dib Mole 10— (4— n-Butylphenyl) 1 10H—Phenoxyxazine, N , N '—bis (4-bromophenyl) 1 N, N ′ —bis (3-ethoxycarbonyl) 1 4, 4, diaminobiphenyl, N, N, 1 diphenyl N, N ′ —bis ( 4-monobromophenyl) —4,4′-diaminobiphenyl and the like.

Aromatic monomers M ³ include 2- (2-Promo 9, 9-dihexyluro 9H—Fluorene 1-7-yl)-1, 3, 2-dioxapololene, 2-— (2-Promo 9, 9 1 x 5,9-dimethyl-1,3,2-dioxapolynan, 2- (2-bromo-9,9-dioctyl 9H-fluorene-7-yl) 1,3,2-Dioxapolynan, 2- (2-Bromo-9,9-didodecyl-9H-fluorene-7 yl) 1,4,4,5,5-tetramethyl-1,3,2-dioxaborolene, 2 ― (2— Black mouth 9, 9-Dihexyluro 9H—Fluorene-7—yl) 1, 4, 4, 5, 5-Tetramethyl 1, 1, 2, 2-dioxaborolen, 2— (4-Bromophenyl) 1, 3, 2—Dioxapolylene, 2-— (4-Promo 2-ethyl 3-methylphenyl) — 1, 3, 2-dioxapolynan, 2— (4-bromo-2-ethoxy-5-isopropylphenyl) 1,5,5-dimethyl-1,3,2-dioxapolynan, 2- (4-cyclophenyl) 1,3,2-dioxaborolene, 2- (4— 1,3-, 2-Dioxapolynan, 2- (4-Clo-neck—2,3-Diisopropylphenyl) -1,3,2-Dioxapololene, 2 -— (3-Petitul 4 1 Chloro-5— (Ethoxyphenyl) — 1, 3, 2—Dioxaborin, 2— [4 'One Promo (1, 1'-Piphenyl)] — 4-Il 1,3,2-Dioxosaporylene, 2— [4 , -Bromo (1, 1, -Phiphenyl)] —4 — 1, 2, 2, Dioxapolynan, 2 — [4, 1 Chloro (1, 1, — Biphenyl)] 1 4 — - Four, 4, .5, 5—Tetramethyl-1,3,2-dioxaborolene, 2— [4, 1- (biphenyl)] —4—yl— 5, 5—dimethyl-1,3 , 2-Dioxapolynan, 2-Bromo-5- (1, 3, 2-Dioxaborolene-2-yl) thiophene, 5-Bromo-5'- (4, 4, 5, 5-tetramethyl-1, 3, 2-Dioxaborolen-2-yl) 1, 2, 2'-bithiophene and the like.

(A) When contacting the aromatic monomer M ¹ and an aromatic monomer one M ² are you producing a conjugated polymer, the reaction of the aromatic monomer M ² to the total number of moles of the boron-containing functional groups of the aromatic monomer M ¹ the ratio of the total moles of sexual functional groups, usually from 8 to 1.2, preferably 0.9 to 1.1, more preferably 0.95 to 1.05 and so as, aromatic monomers M ¹ and aromatic the amount of the monomer M ² is determined.

The palladium catalyst used in the present invention is a palladium catalyst in which a phosphine compound is S-positioned to palladium. As such a palladium catalyst, a commercially available catalyst may be used, or a catalyst prepared by previously contacting a palladium compound and a phosphine compound may be used. The palladium compound and the phosphine compound may contain an aromatic monomer. In addition to the reaction system, it may be prepared in the reaction system.

Palladium catalysts include tetrakis (triphenylphosphine) palladium (0), bis (acetate) bis (triphenylphosphine) palladium (II), bis [1,2-bis (diphenylphosphino) ethane] palladium (0) , [1,2-bis (diphenylphosphino) ethane] dichloropalladium (1 1), dibromobis (triphenylphosphine) palladium (1 1), dichlorobis (dimethylphenylphosphine) palladium (I 1), dichlorobis (methyldiphenyl) Enylphosphine) palladium (I 1), dichlorobis (tricyclohexylphosphine) palladium (I 1), dichlorobis (triethylphosphine) palladium (1 1), dichlorobis (triphenylphosphine) palladium (1 1), dichlorobis [Tris (2-methyl Enyl) phosphine] palladium (I 1), tetrakis (methyl diphenyl phosphine) palladium (0), tetrakis (carboxymethyl Le phosphine to tricyclo) palladium (0), and the like. Palladium compounds include tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) · black mouth form adduct, paradium acetate (I 1), palladium chloride (I 1), (Picyclo [2. 2. 1] Hep Yuichi 2,5-Gen) dichloropalladium (I 1), (2,2'-bipyridyl) dichloropalladium (1 1), bis (acetonitrile) chloronitropalladium (1 1), bis (benzonitrile) dichloropalladium (1 1), bis (acetonitrile) dichloropalladium (I 1), dichloro

(1,5-Cyclooctadiene) Palladium (1 1), Dichloro (ethylenediamine) Paradium (1 1), Dichloro (N, N, Ν ', N' — Tetramethylenediamine) Palladium

(I 1), dichloro (1, 10-phenantine phosphorus) palladium (1 1), palladium (II) acetylacetonate, palladium bromide (1 1), palladium (II) hexafluoroacetylacetonate , Palladium iodide (1 1), Palladium nitrate (1 1), Palladium sulfate (1 1), Palladium trifluoroacetate (1 1, Palladium chloride (IV), Palladium potassium bromide (1 1), Palladium potassium chloride (1 1), sodium chloride palladium (11), tetraamminepalladium nitrate (11), tetrakis (acetonitrile) palladium (II) tetravalent palladium compounds such as tetravalent compounds. Even palladium acetate (1 1), palladium chloride (1 1), tris (dibenzylideneacetone) dipalladium (0), tri (Dibenzylideneacetone) Jiparaji © beam (0) black port Holm adducts are preferred.

A commercially available palladium compound is usually used.

The phosphine compound includes a phosphine compound in which at least one alkyl group is bonded to a phosphorus atom (hereinafter abbreviated as alkylphosphine), three substituted or unsubstituted alkyls.

—A phosphine compound in which a sulfur group is bonded to a phosphorus atom (hereinafter abbreviated as arylephosphine).

Examples of the alkyl phosphine include a monodentate alkyl phosphine having one phosphorus atom bonded to at least one alkyl group, a bidentate alkyl phosphine having two phosphorus atoms bonded to at least one alkyl group, and the like. preferable. Examples of the alkyl phosphine include tricyclohexylphosphine, tributylphosphine, tri-tert-butylphosphine, triisopropylphosphine, triethylphosphine, trimethylphosphine, butyldiadamantylphosphine, adamantyldibutylphosphine, cyclohexyldiisopropylphosphine, isopropyl Dicyclohexylhexylphosphine, tert-butyldicyclohexylphosphine, cyclohexyldi-tert-peptylphosphine, tert-butyldimethylphosphine, di-tert-butylmethylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine , Jetylphenylphosphine, diphenylpropylphosphine, dipropylphenylphosphine, Monodentate alkyl phosphines such as tildiphenylphosphine, diptylphenylphosphine, cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, tert-butyldiphenylphosphine, ditert-butylphenylphosphine, diphenylphosphine Inomethane, 1,2-diphenylphosphinoethane, 1,3-diphenylphosphinopropane, 1,4-diphenylphosphinoethane, 1,2-dicyclohexylphosphinoethane, 1,3-dicyclohexylphosphinopropane 1,4-dicyclohexylphosphinobutane, 1,2-dimethylphosphinoethane, 1,3-dimethylphosphinopropane, 1,4-dimethylphosphinoethane, 1,2-jetylphosphinoethane, 1, 3-Jetylphosphinopropane, 1,4 Phinobutane, 1,2-diisopropylphosphinoethane, 1,3-diisopropylphosphinopropane, 1,4-diisopropylphosphinobutane, 2,3-bis (diphenylphosphino) butane, 2,4 bis (diphenylphosphine) Fino) pentane, 1,2 bis (dipentafluorophenylphosphino) ethane, 1,3-bis (dipentafluorophenylphosphino) propane, 1,4 bis (dipentafluorophenylphosphino) butane, 2- (Dicyclohexylphosphino) Bidentate alkylphosphine such as biphenyl.

Among the monodentate alkyl phosphines, the formula (I) R ¹

(I)

(In the formula, R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 30 carbon atoms.)

Is preferred.

Examples of the alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and decyl group. , Dodecyl group, cyclopentyl group, cyclohexyl group, adamantyl group and the like.

These trialkylphosphines include tricyclohexylphosphine, tributyl phosphine, tri-tert-butylphosphine, triisopropylphosphine, triethylphosphine, trimethylphosphine, butyldiadamantylphosphine, adamantyldibutylphosphine, cyclohexane. Hexyl diisopropyl phosphine, isopropyl dicyclohexyl phosphine, tert-butyl dicyclohexyl phosphine, cyclohexyl tert-butyl phosphine, tert-butyl dimethyl phosphine, di-tert monobutyl methyl phosphine, preferably tricyclohexyl phosphine Are listed.

As the arylphosphine, the formula (I I)

(Wherein R ⁴ , R ⁵ and R ⁶ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms. 1 and m and n each independently represent an integer of 0 to 5. When 1 represents an integer of 2 or more, R ⁴ may be different from each other, and m is an integer of 2 or more. R ⁵ are different from each other May be. When n represents an integer of 2 or more, R ⁶ may be different from each other. In which R ⁴ , R ⁵ and R ⁶ are each independently a fluorine atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. More preferred.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom and a chlorine atom are preferable.

Examples of the alkyl group having 1 to 20 carbon atoms and the alkoxy group having 1 to 20 carbon atoms are the same as those described above.

Such triarylphosphines include triphenylphosphine, 、 ris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphine, tris (4-methylphenyl) phosphine, tris (fluorophenyl) phosphine, tris (4 Monofluorophenyl) phosphine, tris (2-methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2,4,6-trimethoxyphenyl) Examples include phosphine, tris (3-chlorophenyl) phosphine, tris (4-cyclophenyl) phosphine, and the like, and triphenylphosphine and tris (4-methylphenyl) phosphine are preferable.

As such a phosphine compound, a commercially available one may be used, or one produced according to a known method may be used.

(A) The amount of Parajiumu catalyst when contacting the aromatic monomers one M ¹ and an aromatic monomer M ² are you producing a conjugated polymer, versus the sum of the aromatic monomer M ¹ and an aromatic monomer M ² Usually, it is 0.01 to 10 mol%, preferably 0.01 to 5 mol%.

(B) When the conjugated polymer is produced by bringing the aromatic monomers M ³ into contact with each other, the amount of the palladium catalyst used is usually from 0 to 1 to 10 mol%, preferably from the aromatic monomer M ³ . Is 0.01 to 5 mol%.

When the palladium catalyst and the phosphine compound are added to the reaction system containing the aromatic monomer and the palladium catalyst is prepared in the reaction system, the amount of the palladium compound used is the aromatic monomer. —The total amount of M ¹ and the aromatic monomer M ² or the aromatic monomer M ^{3 is} usually from 0.001 to 10 mol%, preferably from 0.01 to 5 mol%, and the use of the phosphine compound The amount is usually 0.2 to 20 mol, preferably 0.8 to 5 mol, relative to 1 mol of the paradium compound. Examples of ether solvents include aliphatic ether solvents such as ethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane. Tetrahydrofuran is preferred. As such an ether solvent, one that has been dehydrated in advance is usually used.

If the amount of the ether solvent used is too large, a conjugated polymer having a low molecular weight is likely to be obtained.If the amount used is too small, the properties of the reaction mixture are likely to deteriorate, so the total amount of aromatic monomers used Usually, it is 1 to 200 times by weight, preferably 5 to 100 times by weight.

A commercially available cesium carbonate is usually used. The amount used is usually 1 mol or more, preferably 2 to 5 mol, per 1 mol of the reactive functional group of the aromatic monomer M ² or the aromatic monomer M ³ .

In the present invention, the polymerization reaction of the aromatic monomer is carried out in the presence of 1 to 100 mol of water with respect to 1 mol of the boron-containing functional group of the aromatic monomer. When a palladium catalyst in which alkylphosphine is coordinated to palladium is used as the palladium catalyst, the polymerization reaction is carried out in the presence of 1 to 75 mol of water for 1 mol of the boron-containing functional group of the aromatic monomer. It is preferable to carry out the polymerization reaction in the presence of 1 to 45 mol of water. When a palladium catalyst in which allylphosphine is coordinated to palladium is used as the palladium catalyst, the polymerization reaction is carried out in the presence of 1 to 25 mol of water for 1 mol of the boron-containing functional group of the aromatic monomer. It is preferable to do.

(A) When the polymerization reaction is carried out by bringing the aromatic monomer M ¹ and the aromatic monomer M ² into contact, usually the aromatic monomer M ¹ , the aromatic monomer M ² , the ether solvent, the palladium catalyst, and cesium carbonate. The polymerization reaction is carried out by mixing water with water. The total amount of the aromatic monomer M ^{1 and} the total amount of the aromatic monomer M ² may be mixed to perform a polymerization reaction, or a part of the aromatic monomer M ¹ used and a part of the aromatic monomer M ² used. by mixing the door, after the polymerization reaction was rows summer, further by mixing the resulting reaction mixture with the remaining aromatic monomer M ¹ and an aromatic monomer M ² Heavy "^ Reaction may be performed.

(B) When carrying out the polymerization reaction by contacting with each other the aromatic monomer M ^3, usually, more polymerization reaction in mixing the aromatic monomer M ³ and ether solvent and a palladium catalyst and cesium carbonate and water is performed The

The polymerization temperature is usually from 0 to 200 ° C., preferably from 10 to 1.20 ° C.

The polymerization time varies depending on the amount of palladium catalyst used, but is usually 1 to 96 hours.

After completion of the polymerization reaction, for example, the conjugated polymer can be precipitated by mixing the obtained reaction mixture with a solvent that does not dissolve or hardly dissolves the conjugated polymer produced. The precipitated conjugated polymer can be separated from the reaction mixture by filtration or the like. The structure and molecular weight of the separated conjugated polymer can be analyzed by ordinary analytical means such as gel permeation chromatography and NMR.

Examples of the solvent that does not dissolve or hardly dissolve the produced conjugated polymer include water, methanol, ethanol, and acetonitrile. Water and methanol are preferable.

Specific examples of the structural unit of the conjugated polymer thus obtained are shown below. In the following formulas, R ^{1 Q} , Y, Z, p, q, r and s represent the same meaning as described above, and when there are a plurality of Z and Y, they may be different from each other.

zz

TlCSS0 / .00Zdf / X3d .08S0T / .00Z OAV

8δ

TlCSS0 / .00Zdf / X3d .08S0T / .00Z OAV

TlCSS0 / .00Zdf / X3d

9Z

TlCSS0 / .00Zdf / X3d .08S0T / .00Z OAV

9Z

TlCSS0 / .00Zdf / X3d .08S0T / .00Z OAV .Example

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The obtained conjugated polymer was analyzed by gel permeation chromatography under the following analysis conditions, and the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were calculated from the obtained analysis results.

G PC measuring device: C TO— 1 OA (manufactured by Shimadzu Corporation)

Column: PLg el 5 MI XE D—C (300 X 7.5 mm) and PL ge 1 5 lim. MI XED—D (300 X 7.5 mm) connected in series (both manufactured by Polymer Rapola Tories) )

Column temperature: 60, mobile phase: tetrahydrofuran, flow rate: Ό. EmLZ min

Detection wavelength: 254 nm Example 1

In a glass reaction vessel equipped with a cooling device, 2, 2- (9,9-dioctylu 9 H—full-year-old ren 2,7-zyl) bis (1,3,2-dioxaborolene) 106 mg, 2, 7- Jib mouth moe 9, 9-didodecyl 9H-fluorene 132 mg, tris (dibenzylidene acetone) dipalladium (0) 4.6 mg, tricyclohexylphosphine 5.6 mg, cesium carbonate 39 lmg, tetrahydrofuran (dehydrated) 2. 99 mL and water 0.01 ml was added. The resulting mixture was refluxed for 6 hours under a nitrogen atmosphere to obtain a reaction mixture containing a synergistic polymer containing the following structural units.

Mw: 326, 000 g / mo Mn: 13 1,000 g / mo 1

Example 2

The same procedure as in Example 1 was carried out except that the amount of tetrahydrofuran (dehydration) used in Example 1 was 2.97 mL and the amount of water used was 0.03 mL. A reaction mixture containing a conjugated polymer containing units was obtained.

Mw: 393,000 g / mo Mn: 184,000 g / mo 1 Example 3

The same procedure as in Example 1 was carried out except that the amount of tetrahydrofuran (dehydration) used was 2.85 mL and the amount of water used was 0.15 mL in Example 1, including the structural unit shown in Example 1. A reaction mixture containing a conjugated polymer was obtained.

Mw: 404, 000 g / mo 1, Μη: 1 96, 000 g / mo 1 Example 4

The same procedure as in Example 1 was carried out except that the amount of tetrahydrofuran (dehydration) used was 2.70 mL and the amount of water used was 0.3 OmL in Example 1, and includes the structural unit shown in Example 1. A reaction mixture containing a conjugated polymer was obtained.

Mw: 322, 000 g / mo K Μη: 140, 000 g / mo 1 Example 5

The same procedure as in Example 1 was carried out except that the amount of tetrahydrofuran (dehydration) used was 2.60 mL and the amount of water used was 0.4 OmL in Example 1. The structural unit shown in Example 1 was included. A reaction mixture containing a conjugated polymer was obtained.

Mw: 221,000 g / mo 1, Mn: 92,000 g / mo 1 Example 6

In Example 1, the amount of tetrahydrofuran (dehydration) used was 2.5 OmL, The reaction mixture containing the conjugated polymer containing the structural unit shown in Example 1 was obtained in the same manner as in Example 1 except that the amount used was 0.5 OmL.

Mw: 162, 000 g / mo 1, Mn: 65, 000 g / mo 1 Example 7

The same procedure as in Example 1 was performed except that the amount of tetrahydrofuran (dehydration) used in Example 1 was 2.4 OmL and the amount of water used was 0.6 OmL. A reaction mixture containing a conjugated polymer containing units was obtained.

Mw: 138, '000 g / mo 1, Mn: 70, 000 g / mo 1 Comparative Example 1' '

In Example 1, except that the amount of tetrahydrofuran (dehydration) used was 3. OmL, and 0.0 lmL of water was not added, the same procedure as in Example 1 was carried out, and the conjugate containing the structural unit shown in Example 1 A reaction mixture containing the polymer was obtained.

Mw: 4,000 g / mo 1> Mn: 3,000 g / mo 1 Comparative Example 2

2, 2— (9,9-dioctyl 9 H—fluorene-1,2,7-diyl) bis (1,3,2-dioxaborolene) 212 mg, 2,7, 1 jib in a glass reaction vessel equipped with a cooling device Mo 9, 9-didodecyl- 91- I-fluorene 264 mg, 1, Lis (dibenzylidene acetone) dipalladium (0) 9.2 mg, tricyclohexylphosphine 1 1.2 mg, cesium carbonate 782 mg, tetrahydrofuran (dehydrated) 5. 99 mL And 0.01 ml of water was added. The resulting mixture was refluxed for 6 hours under a nitrogen atmosphere to obtain a reaction mixture containing a conjugated polymer containing the structural unit shown in Example 1.

Mw: 54, 000 g / mo Mn: 28, 000 g / mo 1 Example 8

In a glass reaction vessel equipped with a cooling device, 2, 2— (9,9-dioctylru 9 H—fluorene-1,2,7-zyl) bis (1,3,2-dioxaborolene) 106 mg, 2, 7—jib Mo 9, 9-didodecyl-9H-fluorene 132 mg, tris (dibenzylidene acetone) dipalladium (0) 4.6 mg, triphenylphosphine 5.2 mg, cesium carbonate 39 lmg, tetrahydrofuran (dehydrated) 2. 97 mL and water 0 Added 03 mL. The resulting mixture was refluxed for 6 hours under a nitrogen atmosphere to obtain a reaction mixture containing a conjugated polymer containing the structural unit shown in Example 1.

Mw: 143,000 g / mo 1, Mn: 63,000 g / mo 1 Example 9 ■

In Example 8, the structural unit shown in Example 1 was used except that the amount of tetrahydrofuran (dehydration) was 2.94 mL and the amount of water was 0.06 mL. A reaction mixture containing a conjugated polymer containing was obtained.

Mw: 170,000 g / mo K Mn: 73,000 g / mo 1 Example 10

The structural unit shown in Example 1 was used in the same manner as in Example 8 except that the amount of tetrahydrofuran (dehydration) used was 2.85 mL and the amount of water used was 0.15 mL in Example 8. A reaction mixture containing a conjugated polymer containing was obtained.

Mw: 125, 000 g / mo Mn: 54, 000 g / mo 1 Comparative Example 3

In Example 8, except that the amount of tetrahydrofuran (dehydration) used was 3. OmL, and 0.03 mL of water was not added, the same procedure as in Example 8 was performed, and the conjugated polymer containing the structural unit shown in Example 1 was used. A reaction mixture containing was obtained. Mw: 20, 000 g / mo Mn: 10,000 g / mo 1 Example 11.

The structural unit shown in Example 1 was used in the same manner as in Example 8 except that the amount of tetrahydrofuran (dehydration) used was 2.70 mL and the amount of water used was 0.3 OmL. A reaction mixture containing a conjugated polymer containing was obtained.

Mw: 69, 000 g / mo 1, Mn: 30,000 g / mo 1 Example 12

In Example 8, carried out in the same manner as in Example 8 except that the amount of tetrahydrofuran (dehydration) used was 2.4 OmL and the amount of water used was 0. '6 OmL; the structure shown in Example 1 A reaction mixture containing a conjugated polymer containing units was obtained.

Mw: 76,000 g / mo Mn: 33,000 g / mo 1 Example 13

In a glass reaction vessel equipped with a cooling device, 2, 2— (9,9-dioctyl 1 9 H-fluorene 1 2, 7-zyl) Bis (1, 3, 2-dioxaborolene) 2. 12 g, 2, 7 -Dive mouth moe 9, 9-didodecyl-9H-fluorene 2.64g, tris (dibenzylideneacetone) dipalladium (0) 11. Omg, triphenylphosphine 12.6g, cesium carbonate 7.82g, tetrahydrofuran (dehydrated) 39. 6 mL and 0.4 mL of water were added. The resulting mixture was refluxed for 48 hours under a nitrogen atmosphere. The resulting reaction mixture was cooled to room temperature, and diluted with 6 OmL of toluene. The diluted reaction mixture was passed through Celite-545 (amount used: 20 g) manufactured by Naoray Lightesque 'to remove the solids. The obtained filtrate was concentrated to obtain 2.65 g of a conjugated polymer containing the structural unit shown in Example 1.

Mw: 160, 000 g / mo 1> Mn: 67, 000 g / mo 1 Example 14

In Example 8, instead of triphenylphosphine 5.2 mg, tris (4-methylphenyl) phosphine 6. lmg was used, except that the structural unit shown in Example 1 was obtained. A reaction mixture containing a conjugated polymer was obtained.

Mw: 178, 000 gZmo 1, Mn: 75,000 g / mo 1 Example 15

In a glass reaction vessel equipped with a cooling device, 2, 2— (9,9-dioctyl-9 H-fluorene-2,7-zyl) bis (1,3,2-dioxapololene) 106 mg, 4, 7-dibromo-2,1,3-benzoythiadiazole 59mg, tris (dibenzylideneacetone) dipalladium (0) 4.6mg, tricyclohexylphosphine 5.6mg, cesium carbonate 391mg, tetrahydrofuran (dehydrated) 2 97 mL and 0.03 mL of water were added. The resulting mixture was refluxed for 6 hours under a nitrogen atmosphere to obtain a reaction mixture containing a conjugated polymer containing the following structural units.

Mw: 214, 000 g / mo Mn: 98, 000 g / mo 1

Example 16

In a glass reaction vessel equipped with a cooling device, 2, 2— (9,9-dioctylru 9 H—full-year-old ren 2,7-gil) bis (1,3,2-dioxaborolene) 106 mg, 4, 7-dibu Mouth Mo 2, 1,3-benzothiadiazole 59mg, Tris (dibenzylideneacetone) dipalladium (0) 4.6 mg, Triphenylphosphine 5.2 mg, Cesium carbonate 39 lmg, Tetrahydrofuran (dehydrated) 2. 97 mL and water 0.03 mL was added. The resulting mixture is refluxed for 6 hours under a nitrogen atmosphere and contains the structural units shown in Example 15. A reaction mixture containing a conjugated polymer was obtained.

Mw: 108, 000 g / mo Μη: 45, 000 g / mo 1 Comparative Example 4

In a glass reaction vessel equipped with a cooling device, tetrakis (triphenylphosphine) paradium (0) 29mg, 2M aqueous potassium carbonate solution 3mL, 2, 2- (9,9-dioctyl 9H-fluorene-2,7-diyl ) Bis (1,3,2-dioxaborolene) 265 mg, 4,7-jib mouth moe 2,1,3-benzothiadiazol 147 mg and tetrahydra mouth furan (dehydrated) 2. O OmL was added. The resulting mixture was refluxed for 6 hours under a nitrogen atmosphere to obtain a reaction mixture containing a conjugated polymer containing the structural unit shown in Example 15.

Mw: 5,000 g / mo 1, Mn: 3,000 g / mo 1 Comparative Example 5

In a glass reaction vessel equipped with a cooling device, tetrakis (triphenylphosphine) paradium (0) 23 mg, 2 M aqueous sodium carbonate solution 3.0 mL, A 1 iquat 336 (manufactured by Aldrich) 8 mg, 2, 2— (9,9-dioctyl-9H-fluorene-1-2,7-diyl) bis (1,3,2-dioxaborolene) 212mg, 4,7-dibromo-2,1,3-benzothiadiazole 118mg and toluene 3.O OmL added. The resulting mixture was refluxed for 6 hours under a nitrogen atmosphere to obtain a reaction mixture containing a conjugated polymer containing the structural unit shown in Example 15.

Mw: 53,000 g / mo 1, Mn: 23,000 g / mo 1 Example 17

In a glass reaction vessel equipped with a cooling device, 2, 2- (9,9-dioctyl-9H-fluorene-1,7-zyl) bis (1,3,2-dioxaborolene) 106mg, N, N ' —Di (4 bromophenyl) — N, N′-di (3-ethoxycarbonyl) 1 4, 4'-diaminobiphenyl 158 mg, tris (dibenzylideneacetone) dipalladium (0) 4.6 mg, tricyclohexylphosphine 5.6 mg, cesium carbonate 39 lmg, tetrahydrofuran (dehydrated) 2. 9701 Was added. The resulting mixture was refluxed for 6 hours under a nitrogen atmosphere to obtain a reaction mixture containing a conjugated polymer containing the following structural units.

Mw: 183, 000 g / mo 1> Mn: 57, 000 g / mo 1

Comparative Example 6

In Comparative Example 4, instead of 147 mg of 4,7-dibromo-2,1,3-benzobenzodiazol, ゾ, Ν 'bis (4-promophenyl) Ν Ν, N' bis (3— Ethoxycarbonyl) —4,4′-diaminobiphenyl 395. The same procedure as in Comparative Example 4 was carried out except that 3 mg was used to obtain a reaction mixture containing a conjugated polymer containing the structural unit shown in Example 17. .

Mw: 40,000 g / mo 1, Mn: 20, 000 g / mo 1 Comparative Example 7

In Comparative Example 5, instead of 118 mg of 4,7-jib mouth-moe 2, 1,3-benzazothiadiazole, N, N, monobis (4-bromophenyl) mono N, N, monobis (3-ethoxyca Luponyl phenyl) 1, 4, 4, Diaminobiphenyl 316. Compared with 2 mg In the same manner as in Example 5, a reaction mixture containing a conjugated polymer containing the structural unit shown in Example 17 was obtained.

Mw: 20,000 g / mo 1, Mn: 10,000 g / mo 1 Example 18

In a glass reaction vessel equipped with a cooling device, 2, 2- (9,9-dioctyl-9 H-fluorene-1,2-diyl) bis (1,3,2-dioxaborolene) 106 mg, 1, -dipromonaphthalene 57 mg, tris (dibenzylideneacetone) dipalladium (0) 4.6 mg, trisic hexylphosphine 5.6 mg, cesium carbonate 39 lmg, tetrahydrofuran (dehydrated) 2.97 mL and water 0.03 mL were added. The resulting mixture was refluxed for 6 hours under a nitrogen atmosphere to obtain a reaction mixture containing a conjugated polymer containing the following structural units.

Mw: 139, 000 g / mo K Mn: 55,000 g / mo 1

Comparative Example 8

In Comparative Example 4, the same procedure as in Comparative Example 4 was carried out except that 143 mg of 1,4 1-dibu mouth monaphthalene was used instead of 147 mg of 4,7-dibromo-2,1,3-benzothiadiazole. A reaction mixture containing a conjugated polymer containing the structural units shown in Example 18 was obtained.

Mw: 12,000 g / mo 1, Mn: 6,000 g / mo 1 Comparative Example 9

In Comparative Example 5, it was carried out in the same manner as Comparative Example 5 except that 114 mg of 1,4 1-dib mouth monaphthalene was used instead of 118 mg of 4,7-jib mouth mo 2,1,3-benzothiadiazol, A reaction mixture containing a conjugated polymer containing the structural unit shown in Example 18 was obtained. Mw: 84,000 g / mo Mn: 36,000 g / mo 1 Example 19

In a glass reaction vessel equipped with a cooling device, 2, 2— (9,9-dioctylru 9 H—fluorene-1,2,7-diyl) bis (1, 3, 2-dioxaborolene) 106 mg, 2, 7—jib mouth Mo 9,9-didodecyl-9 H-fluorene 93 mg, 3,5-dibromopyridine 14 mg, tris (dibenzylideneacetone) dipalladium (0) 4.6 mg, trisic hexylphosphine 5.6 mg, cesium carbonate 39 lmg, tetrahydrofuran (Dehydration) 2. 97 mL and 0.03 mL of water were added. The resulting mixture was refluxed for 6 hours under a nitrogen atmosphere to obtain a reaction mixture containing a conjugated polymer containing the following structural units.

Mw: 169,000 g / mo K Mn: 80,000 g / mo 1

Comparative Example 10

In Comparative Example 4, 3,7-dibromopyridine 36 mg and 2,7-dibromo-9,9-didodecyl-9 H-fluorene instead of 147 mg of 4,7-dibu mouth mo 2,1,3-benzothiadiazol The reaction was carried out in the same manner as in Comparative Example 4 except that 23 lmg was used to obtain a reaction mixture containing a conjugated polymer containing the structural unit shown in Example 19.

Mw: 72,000 g / mo 1, Mn: 31, 000 g / mo 1 Example 20

In a glass reaction vessel equipped with a cooling device, 2, 2- (9, 9-dioctyl 9 H-fluorene-2, 7-zyl) bis (1, 3, 2-dioxapololene) 106 mg, 2, 7-dibu Mouth Mo 9, 9—Didodecyl—9H—Fluorene 106 mg, 2, 5—Jib Mouth 3— Hexylthiophene 13 mg, tris (dibenzylideneacetone) dipalladium (0) 4.6 mg, tricyclohexylphosphine 5.6 mg, cesium carbonate 391 mg, tetrahydrofuran (dehydrated) 2.97 mL and water 0.03 mL were added. The resulting mixture was refluxed for 6 hours under a nitrogen atmosphere to obtain a reaction mixture containing a conjugated polymer containing the following structural units.

Mw: 177, 000 g / mo Mn: 71, 000 g / mo 1

Comparative Example 11

In Comparative Example 4, instead of 147 mg of 4,7-dibromo 2,1,3-benzothiadiazol, 2,5-dibromo-3-hexylthiophene 46.9 mg and 2,7-dipromo 9, 9- A reaction mixture containing a conjugated polymer containing the structural unit shown in Example 20 was obtained in the same manner as in Comparative Example 4 except that 23 lmg of didodecyl-9H-fluorene was used.

Mw: 47,000 g / mo Mn: 21,000 g / mo 1 Example 21

In a glass reaction vessel equipped with a cooling device, 2, 2-(9,9-dioctyl-9H-full-year-old 2,1-diyl) bis (1,3,2-dioxaborolene) 106mg, 2, 7 — Jib mouth moe 9, 9-didodecyl 9H—fluorene 93 mg, 4, 7-bis (5-promo —2-cenyl) 1, 2, 1, 3-benzothiazole 27 mg, tris (dibenzylidene seton) dipalladium (0 ) 4.6 mg, tricyclohexylphosphine 5.6 mg, cesium carbonate 391 mg, tetrahydrofuran (dehydrated) 2. 97 mL and water 0.03 mL were added. The resulting mixture was refluxed for 6 hours under a nitrogen atmosphere to obtain a reaction mixture containing a conjugated polymer containing the following structural units.

Mw: 156, 000 g / mo 1 Mn: 72, 000 g / mo 1

Comparative Example 12

In Comparative Example 4, instead of 147 mg of 4,7-dibromo-2,1,3-benzothiadiazole, 4,7-bis (5-bromo-2-chenyl) —2,1,3-benzothiadiazole 69 mg and The same procedure as in Comparative Example 4 was conducted except that 231 mg of 2,7-dibromo-9,9-didodecyl-9 H-fluorene was used, and a reaction mixture containing a conjugated polymer containing the structural unit shown in Example 21 was obtained. .

Mw: 71, 000 g / mo Μη: 30,000 g / mo 1 Example 22

In a glass reaction vessel equipped with a cooling device, 2, 2 '-(1, 4-phenylene) bis (5, 5-dimethyl-1, 3, 2-dioxaborinane) 60 mg, 2, 7-dibromo-9 9-didodecyl 9H-fluorene 132mg, tris (dibenzylideneacetone) diparadium (0) 4.6mg, tricyclohexylphosphine 5.6mg, cesium carbonate 391mg, tetrahydrofuran (dehydrated) 2.97mL and water 0.03mL added. Under a nitrogen atmosphere, the obtained mixture was refluxed for 6 hours to obtain a reaction mixture containing a conjugated polymer containing the following structural units.

Mw: 272, 000 g / mo 1 Mn: 132, 000 g / mo 1

Comparative Example 13 In Comparative Example 4, 2,7-dibromo-9,9-didodecyl-9H-fluorene 33 Omg was used in place of 147 mg of 4,7-dibromo-2,1,3-benzobenzodiadiazole, 2, 2- ( 9, 9-Dioctyl 9 H-Fluorene-1, 2, 7-diyl) Bis (1, 3, 2-dioxapololene) Instead of 265 mg, 2, 2 '-(1, 4-phenylene) bis (5, 5— A reaction mixture containing a conjugated polymer containing the structural unit shown in Example 22 was obtained in the same manner as in Comparative Example 4 except that 15 mg of (dimethyl-1,3,2-dioxapolynan) was used.

Mw: 94,000 g / mo 1 Mn: 33,000 g / mo 1 Industrial applicability „According to the production method of the present invention, a conjugated polymer having a high molecular weight can be produced.

Claims

The scope of the claims

1. (A) an aromatic monomer having at least two boron-containing functional groups and an aromatic monomer having at least two reactive functional groups, or (B) at least one boron-containing functional group and at least 1 Aromatic monomers having two reactive functional groups are combined with each other in a ether catalyst with a palladium catalyst in which a phosphine compound is coordinated to palladium, cesium carbonate, and 1 mol of the boron-containing functional group of the aromatic monomer. A method for producing a conjugated polymer, which comprises contacting in the presence of ˜100 mol of water.

2. The method for producing a conjugated polymer according to claim 1, wherein the ether solvent is an aliphatic ether solvent. ·

3. The method for producing a conjugated polymer according to claim 2, wherein the aliphatic ether solvent is tetrahydrofuran.

4. The method for producing a conjugated polymer according to any one of claims 1 to 3, wherein the phosphine compound is a phosphine compound in which at least one alkyl group is bonded to a phosphorus atom.

5. A phosphine compound having at least one alkyl group bonded to a phosphorus atom is represented by the formula (I)

R ¹

(I)

5. The method for producing a conjugated polymer according to claim 4, wherein the conjugated polymer is a trialkylphosphine represented by the following formula.

6. The method for producing a conjugated polymer according to claim 5, wherein the trialkylphosphine represented by the formula (I) is tricyclohexylphosphine.

7. Production of the conjugated polymer according to any one of claims 4 to 6, wherein the boron-containing functional group of the aromatic monomer is brought into contact with 1 to 75 mol of water in the presence of 1 to 75 mol of water. Method.

8. Production of the conjugated polymer according to any one of claims 4 to 6, wherein the boron-containing functional group of the aromatic monomer is brought into contact with 1 to 45 mol of water in the presence of 1 to 45 mol of water. Method.

9. The method for producing a conjugated polymer according to any one of claims 1 to 3, wherein the phosphine compound is a phosphine compound in which three substituted or unsubstituted aryl groups are bonded to a phosphorus atom.

1 0. A phosphine compound in which three substituted or unsubstituted aryl groups are bonded to a phosphorus atom is represented by the formula (I I) '

(Wherein R ⁴ , R ⁵ and R ⁶ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms. 1, m and n each independently represents an integer of 0 to 5. When 1 represents an integer of 2 or more, R ⁴ may be different from each other, m is an integer of 2 or more. And R ⁵ may be different from each other, and when n represents an integer of 2 or more, R ⁶ may be different from each other. Of producing a conjugated polymer.

11. The method for producing a conjugated polymer according to claim 10, wherein the phosphine compound represented by the formula (I I) is triphenylphosphine or tris (4-methylphenyl) phosphine.

1 2. 1 to 25 mol of water per mol of boron-containing functional group of the aromatic monomer The method for producing a conjugated polymer according to any one of claims 9 to 11, which is contacted in the presence of.

1 3. Aromatic monomer having at least two boron-containing functional groups, aromatic monomer having at least two reactive functional groups, and fragrance having at least one boron-containing functional group and at least one reactive functional group Group monomers are represented by the formulas

(6)

(Wherein, X ¹ and X ² each independently represent a boron-containing functional group or a reactive functional group, R ^1Q represents a group not involved in the reaction, p represents an integer of 0 to 2, q represents an integer of 0 to 3, r represents an integer of 0 to 4, and s represents an integer of 0 to 5. R ^{1 (} may be different from each other when there are a plurality of ⁵ or aromatic rings. Two R ^1Q bonded to adjacent carbon atoms of each other may be bonded together to form a ring together with the bonded carbon atoms Y represents a group 16 element in the periodic table, Z is 101, 1 S-, 1 N (R ²⁰ ) 1 or

R ²¹ヽ R ²²

Represents. Where R ^2Q , R ²¹ and R ²² are each independently a hydrogen atom or reaction Represents a non-participating group. )

The method for producing a conjugated polymer according to claim 1, wherein the conjugated polymer is any one of the following aromatic monomers: ·

14. The method for producing a conjugated polymer according to claim 1 or 13, wherein the reactive functional group is a chlorine atom, a bromine atom or an iodine atom.

15. The boron-containing functional group

(In the formula, R ³⁰ , R ³¹ , R ³⁴ and R ³⁵ each independently represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ³³ represents a divalent hydrocarbon group. Represents.)

14. The method for producing a conjugated polymer according to claim 1 or 13, wherein the conjugated polymer is any one of the following groups.

16. The method for producing a conjugated polymer according to claim 15, wherein the divalent hydrocarbon group is an alkylene group having 2 to 6 carbon atoms.

17. An alkylene group having 2 to 6 carbon atoms is an even — 1, 2— diyl group, a propane — 1, 3-diyl group, a 2, 2-dimethylpropane 1, 3, 3- diyl group, or a 2, 3— The method for producing a conjugated polymer according to claim 16, which is a dimethylbutane-1,3-diyl group.